Water-insoluble azo-dyestuffs and fiber dyed therewith



Patented Oct. 9, 1934 UNITED STATES PATENTQFFKCE WATER-INSOLUBLE AZO-DYESTUFFS AND FIBER DYED THEREWITH Carl Josef Miiller and Werner Kirst, Frankforton-the-Main, Germany, assignors to General Aniline Works, ;Inc., tion of Delaware New York, N. Y., a corpora- No Drawing. Application October 5, 1931, Serial Q No. 567,131. In Germany October 6, 1930 14 Claims.

The present invention relates to new water-insoluble azo-dyestuffs and to fiber dyed therewith, more particularly it relates to green water-insoluble azo-dyestufis which are obtainable by combining a diazo-compound of '7,7'-diaminothioindigo and its substitution products with an acetyl-acetic-acid-arylide.or an aroyl-aceticacid. arylider v ,j

We have found that green azo-dyestufis areob- .tainable by combining the above diazo-compounds of the indigoid vat-dyestuff with the said 7 thermore, benzoyl-acetic-acid-arylides, dibenzoyl-acetic-acid-arylides, terephthaloyl-bis-acetic-acidarylides and their substitution :products,

may be used. Y Y

The new water-insoluble azo-dyestuifs obtainable from diazotized '7,7'-diaminothioindigo sur-,

pass with regard to their fastness to washing and to soaping the green sulfur-dyestuffs and are distinguished by great tinctorial p'owen The dyestuffs obtained by the present invention are characterized by the following probable general formula:

wherein R, represents alkyl'or a radical of the benzene or naphthalene series, R1 represents a radical of the benzene or naphthalene series and X stands for hydrogen or the radical of the fol lowing formula:

wherein R and R1 have the above indicated meaning, the radicals, however, being free from groups which would make the dyestuffs soluble in water.

The present invention is illustrated by a number of examples; it is pointed out, however, that the combinations mentioned in these examples and the several components used for their preparation only serve as illustrations and that the invention is not limited to the examples contained in this specification. As regards the components: designated as yellow components and. used for.

coupling with the diazo compounds of 7,'7-di aminothioindigo, the invention, likewise, is not restricted to the particular components mentioned in the following examples.

The following examples serve to invention] f (1) Green dyeing on cotton from acetoacetyl-, para-aminophenylsbenzimidazole; and. 7,,'Z-diamillustrate the inothioindigo.

The fiber is impregnated with the following grounding liquor, well hydroextracted or squeezed and dyed in the diazo solution. The material is then rinsed well and soaped at the'boil.

(a) Grounding liquor 5 grams of acetoacetyl-para-aminophenylbenzimidazole', are dissolved with 10 cc. of Turkey red Oil of strength, 10' cc. "of'caustie soda solution of 34 B. and 28 grams of sodium sulfate. This solution is made up with water to 1 liter.

1.63 grams of LT-diamihothioindigo are diazotized with 4 cc[ of hydrochloricacid of 20? B.

and lgram, of sodium nitrite, dissolved iniwater. (Diazotization temperature 20 C. to 30, C.)

Thereupon 6 grams of sodium acetate, l color acetic acid of 98% strength and 25 grams of sodium chloride are added. The whole is made up with water to 1 liter. (Dyeing temperature 30 C. to 40 C.)

A vivid green dyeing of good fastness to soaping is obtained.

- oo oo NE: R

(b) Diazo solution The diazo solution is prepared as in Example 1. A green dyeing of good fastness to washing and to soaping is obtained.

The dyestufi has the following probable formula:

CO OT s s N II N The dyestuif has the following probable formula:

ll N N OHPOOaHHH OH (2) Olivegreen dyeing on cotton from benzoylacetic-acid-para-amidophenylbenzimidazole.

(a) Grounding liquor 5 grams of benzoylacetic-acid-para-amido- (4) By using in Example 1 instead of acetoacetyl-para-aminophenylbenzimidazole acetoacetyl-para-aminophenyl-4-methylbenzimidazole, a similar green dyeing is obtained.

The dyestuff has the following probable formula:

phenylbenzimidazole are dissolved with 10 cc. of Turkey red oil of 50% strength, 15 cc. of caustic soda solution of 34 B. and 28 grams of sodium sulfate. This solution is made up with water to 1 liter.

(b) Diazo solution The diazo solution is prepared as in Example 1.

An olivegreen dyeing of good fastness to washing and to soaping is obtained.

The dyestufi has the following probable formula:

NE: E

(3) Green dyeing on cotton from diacetoacetyl-ortho -tolidine and 7,7 -diaminothioindigo.

(a) Grounding liquor 3 grams of diacetoacetyl-ortho-tolidine are dissolved with 10 cc. of Turkey red oil of 50% strength, 10 cc. of caustic soda solution of 34 B. and 28 grams of sodium sulfate. This solution is made up with water to 1 liter.

green color. The dyestuif has the same probable formula as indicated in Example 3.

The following table indicates a number of green dyestufis obtainable according to the present process but does not comprise all possibilities for the preparation of green to olive-green dyestuffs by using other coupling components, which components, however, must be free from groups which would render the dyestuffs soluble in water; it,

therefore, is not intended to limit the invention to the dyestufis mentioned therein:

Diazotizing component:

Coupling component:

(1) 7, 7-diami.nothioindigo (2) 7, 7-diaminothioindigo (3) 7, 7-diaminothioindigo (4) 7, 7-diaminothioindigo (5) 7, 7-diaminothioindigo (6) 7, 7-diaminothioindigo (7) 7, 7-diaminothioindigo (8) 7, 7-diaminothioindig0 (9) 7, 7'-diaminothioindigo Benzoyl acetic acid ortho chloranilide Para methylbenzoyl acetic acid-alpha-naphthylamide Para-methoxybenzoyl-aceticacid-anilide Meta nitrobenzoyl acetic acid-ortho-chloranilide Beta-naphthoyl-acetic-acidanilide Aceto-acetic-acid-2-methoxy- 4-chloro-l-anilide Terephthaloyl bis acetic acid-4-chloro-2-methoxyanihde Para methylbenzoyl acetic acid-4-methoxy-l-anilide Para chlorobenzoyl acetic acld-amhde (l0) 7, 7'-diaminothioindigo Benzoyl acetic acid ortho toluidide 2. The water-insoluble azo-dyestufis of the following general formula: v

wherein R represents methyl or a radical of the benzene series which may be substituted by alkyl, alkoxy, halogen or the nitro group, R1 represents a radical of the benzene series and X stands for hydrogen or the radical of the following formula:

wherein R and R1 have the above indicated meaning, dyeing green to olivegreen shades of good the dyestuffs to alkalies. Substituents of this fastness properties. kind are, for instance, the sulfonic acid and the 3. The water-insoluble azo-dyestuif of the folcarboxylic acid group. Such groups are not inlowing formula:

NH: I NH: 151' I N I CH O0CH00NHO-NHC O-H-O 0-011; 1130 \CH;

eluded within the scope of the appended claims.

We claim: 1. The water-insoluble azo-dyestulfs of the following general formula:

| NH2 51' N wherein R represents alkyl or a radical of the benzene or naphthalene series, R1 represents a radical of the benzene or naphthalene series and X stands for hydrogen or the radical of the following formula:

l R1NHC O-GH-O O-R wherein R and R1 have the above indicated meaning, dyeing green to olivegreen shades of good fastness properties.

dyeing a green shade of good fastness to washing and to soaping.

4. The water-insoluble azo-dyestuffs of the following general formula:

of the following formula:

wherein Y represents hydrogen or alkyl, dyeing green to olivegreen shades of good fastness properties.

' lowing formula:

'5. The water-insoluble azo-dyes'tuffs of the following general formula: V. I

wherein R1 represents a radical of the benzene series which may be substituted by alkyl, halogen, alkoxy or the radical of'the following formula:

. N v l Y -OH l N wherein Y represents hydrogen or methyl, dyeing green to olivegreen shades of good fastness properties.

6. The water-insoluble azo-dyestuif of the folll N N 0113-0 o-cH-o O-NHOGH 1 dyeing a vivid green shade of good fastness to soaping.

8. Fiber dyed with the dyestufis as claimed in claim 1.

9. Fiber dyed with the dyestuffs as claimed in claim 2.

10. Fiber dyed with the dyestufi as claimed in claim 3.

11. Fiber dyed with the dyestuffs as claimed in claim 4.

12. Fiber dyed with the dyestuffs as claimed in claim 5.

13. Fiber dyed with the dyestufi as claimed in claim 6. I

14. Fiber dyed with the .dyestufi as claimed in claim '7.

CARL JOSEF Mt'iLLER. WERNER KIRST. 

